公开(公告)号：US08916674B2

公开(公告)日：2014-12-23

申请号：US13504064

申请日：2010-12-10

申请人： Zhongwen Wu ,  Rongtang Ma ,  Xiangbin Zeng

发明人： Zhongwen Wu ,  Rongtang Ma ,  Xiangbin Zeng

IPC分类号： C08G75/00 ,  C08G75/23

CPC分类号： C08G75/23

摘要： A method for preparing series of terpolymer of poly (diphenyl ether sulfone) and poly (diphenyl ether diphenyl sulfone) comprises: adding high temperature organic solvent, stirring and heating; sequentially adding 4,4′-dihydroxydiphenyl, 4,4′-dichlorodiphenyl sulfone and 4,4′-Bis(4-chlorophenyl)sulfonyl-1,1′-biphenyl; after all the monomers are completely dissolved, heating to 100° C. and adding alkali metal carbonate salt-forming agent which is 5-10 mol % more than the amount of 4,4′-dihydroxydiphenyl added, and subsequently adding xylene; continuously heating and salt-forming reaction begins in the system, and controlling the temperature at 190˜210° C.; then heating to 230˜236° C., and maintaining for 3-4 hours to obtain polymer viscous liquid; and refining the polymer viscous liquid to obtain a terpolymer containing different structural units in the molecular chain, wherein the Tg of the terpolymer can be regulated by changing the ratio of the two dichloro-containing monomers.

摘要翻译： 一种制备聚（二苯基醚砜）和聚（二苯醚二苯基砜）三元共聚物的方法包括：加入高温有机溶剂，搅拌加热; 依次加入4,4'-二羟基二苯基，4,4'-二氯二苯砜和4,4'-双（4-氯苯基）磺酰基-1,1'-联苯; 在所有单体完全溶解后，加热至100℃，加入碱金属碳酸盐形成剂，其比加入的4,4'-二羟基联苯的量多5-10mol％，随后加入二甲苯; 在系统中开始连续加热和成盐反应，并控制温度在190〜210℃。 然后加热至230〜236℃，保持3-4小时得到聚合物粘稠液体; 并精炼聚合物粘性液体以获得在分子链中含有不同结构单元的三元共聚物，其中三元共聚物的Tg可以通过改变两种含二氯单体的比例来调节。

公开(公告)号：US20120095182A1

公开(公告)日：2012-04-19

申请号：US13318195

申请日：2010-06-23

申请人： Zhongwen Wu ,  Rongtang Ma

发明人： Zhongwen Wu ,  Rongtang Ma

IPC分类号： C08G8/02

CPC分类号： C08G65/4012 ,  C08G65/4093 ,  C08G2650/40

摘要： A method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology comprises: (1) adding high-temperature organic solvent into a three-necked flask equipped with a thermometer, a nitrogen-feeding pipe, and a stirrer; then stirring and heating; orderly adding 4,4′-difluordiphenylketone, 4,4′-bifluorotriphenyldione, hydroquinone, and 4,4′-dihydroxydiphenylketone after the high-temperature organic solvent has been melted, and stirring to completely dissolve them; adding alkali carbonate of 1-5% excessive amount relative to total mole of hydroquinone and 4,4′-dihydroxydiphenylketone; heating to 220-230° C. while stirring, and maintaining the temperature for 20-40 minutes to complete the first salt-forming reaction, (2) heating to 250-260° C., and maintaining the temperature for 20-40 minutes to complete the second salt-forming reaction, (3) heating to 300-320° C. to start condensation polymerization, and maintaining the temperature for 3-4 hours to complete the polymerization, and (4) pouring the obtained polymer solution into distilled water at room temperature to cool to strip-shaped solid, pulverizing, extracting with ethanol to remove organic solvent, extracting with deionized water to remove byproduct salts, and vacuum-drying to obtain quaternary copolymer containing PEEK, PEEKK, PEK, and PEKEKK repeating units in molecule chains. When the mole ratio of hydroquinone to 4,4′-dihydroxydiphenylketone is above 99:1 and the mole ratio of 4,4′-difluorodiphenylketone to 4,4′-bifluorotriphenyldione is above 99:1, the obtained quaternary copolymer mainly contains PEEK chain segments, and has the same macrophysical properties as those of PEEK.

摘要翻译： 通过使用季共聚技术制备聚芳醚酮共聚物的方法包括：（1）将高温有机溶剂加入到配备有温度计，氮气供给管和搅拌器的三颈烧瓶中; 然后搅拌加热; 在高温有机溶剂熔融后，顺序加入4,4'-二氟二苯基酮，4,4'-二氟三苯基二酮，氢醌和4,4'-二羟基二苯基酮，并搅拌使其完全溶解; 加入相对于氢醌和4,4'-二羟基二苯酮的总摩尔量过量1-5％的碱金属碳酸盐; 在搅拌下加热至220-230℃，并保持温度20-40分钟以完成第一次成盐反应，（2）加热至250-260℃，并保持温度20-40分钟 完成第二次成盐反应，（3）加热至300-320℃进行缩聚反应，保持温度3-4小时完成聚合，（4）将得到的聚合物溶液倒入蒸馏水 水在室温下冷却至条状固体，粉碎，用乙醇萃取除去有机溶剂，用去离子水萃取除去副产物盐，真空干燥得到含PEEK，PEEKK，PEK和PEKEKK重复单元的季共聚物 在分子链中。 当氢醌与4,4'-二羟基二苯基酮的摩尔比大于99:1时，4,4'-二氟二苯基酮与4,4'-二氟三苯基二酮的摩尔比为99:1以上，得到的四元共聚物主要含有PEEK链 具有与PEEK相同的大理石物理性质。

公开(公告)号：US08981034B2

公开(公告)日：2015-03-17

申请号：US13318195

申请日：2010-06-23

申请人： Zhongwen Wu ,  Rongtang Ma

发明人： Zhongwen Wu ,  Rongtang Ma

IPC分类号： C08G8/02 ,  C08G14/00 ,  C08G65/40

CPC分类号： C08G65/4012 ,  C08G65/4093 ,  C08G2650/40

摘要： A method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology comprises: (1) adding high-temperature organic solvent into a three-necked flask equipped with a thermometer, a nitrogen-feeding pipe, and a stirrer; then stirring and heating; orderly adding 4,4′-difluordiphenylketone, 4,4′-bifluorotriphenyldione, hydroquinone, and 4,4′-dihydroxydiphenylketone after the high-temperature organic solvent has been melted, and stirring to completely dissolve them; adding alkali carbonate of 1-5% excessive amount relative to total mole of hydroquinone and 4,4′-dihydroxydiphenylketone; heating to 220-230° C. while stirring, and maintaining the temperature for 20-40 minutes to complete the first salt-forming reaction, (2) heating to 250-260° C., and maintaining the temperature for 20-40 minutes to complete the second salt-forming reaction, (3) heating to 300-320° C. to start condensation polymerization, and maintaining the temperature for 3-4 hours to complete the polymerization, and (4) pouring the obtained polymer solution into distilled water at room temperature to cool to strip-shaped solid, pulverizing, extracting with ethanol to remove organic solvent, extracting with deionized water to remove byproduct salts, and vacuum-drying to obtain quaternary copolymer containing PEEK, PEEKK, PEK, and PEKEKK repeating units in molecule chains. When the mole ratio of hydroquinone to 4,4′-dihydroxydiphenylketone is above 99:1 and the mole ratio of 4,4′-difluorodiphenylketone to 4,4′-bifluorotriphenyldione is above 99:1, the obtained quaternary copolymer mainly contains PEEK chain segments, and has the same macrophysical properties as those of PEEK.

摘要翻译： 通过使用季共聚技术制备聚芳醚酮共聚物的方法包括：（1）将高温有机溶剂加入到配备有温度计，氮气供给管和搅拌器的三颈烧瓶中; 然后搅拌加热; 在高温有机溶剂熔融后，顺序加入4,4'-二氟二苯基酮，4,4'-二氟三苯基二酮，氢醌和4,4'-二羟基二苯基酮，并搅拌使其完全溶解; 加入相对于氢醌和4,4'-二羟基二苯酮的总摩尔量过量1-5％的碱金属碳酸盐; 在搅拌下加热至220-230℃，并保持温度20-40分钟以完成第一次成盐反应，（2）加热至250-260℃，并保持温度20-40分钟 完成第二次成盐反应，（3）加热至300-320℃进行缩聚反应，保持温度3-4小时完成聚合，（4）将得到的聚合物溶液倒入蒸馏水 水在室温下冷却至条状固体，粉碎，用乙醇萃取除去有机溶剂，用去离子水萃取除去副产物盐，真空干燥得到含PEEK，PEEKK，PEK和PEKEKK重复单元的季共聚物 在分子链中。 当氢醌与4,4'-二羟基二苯基酮的摩尔比大于99:1时，4,4'-二氟二苯基酮与4,4'-二氟三苯基二酮的摩尔比为99:1以上，得到的四元共聚物主要含有PEEK链 具有与PEEK相同的大理石物理性质。

公开(公告)号：US08389665B2

公开(公告)日：2013-03-05

申请号：US13501356

申请日：2010-10-26

申请人： Zhongwen Wu ,  Rongtang Ma

发明人： Zhongwen Wu ,  Rongtang Ma

IPC分类号： C08G64/00 ,  C08G63/02

CPC分类号： C08G75/23

摘要： A method for preparing terpolymer of poly (biphenyl sulfone ether) and poly (ether sulfone) comprises: adding high-temperature organic solvent into a flask, stirring and heating to 80° C., adding 4,4′-dichlorodiphenylsulfone,4,4′-Bis(4-chlorophenyl)sulfonyl-1,1′-biphenyl and 4,4′-dihydroxydiphenylsulfone with solid content of 20-35%; stirring until monomers are completely dissolved, heating to 100° C., adding salt-forming agent and xylene; stirring while heating so that salt-forming reaction begins in the system, wherein the system temperature is controlled between 190° C. and 210° C.; when the amount of water discharged reaches the theoretical value, the first stage of salt-forming reaction is finished; heating the system to 230-236° C., and maintaining for 3-4 hours to obtain polymer viscous liquid; and refining the polymer viscous liquid to obtain a terpolymer containing different structural units in the molecular chain, wherein the Tg of the terpolymer can be regulated by changing the ratio of the two dichloro-containing monomers.

摘要翻译： 制备聚（联苯砜醚）和聚（醚砜）三元共聚物的方法包括：向烧瓶中加入高温有机溶剂，搅拌加热至80℃，加入4,4'-二氯二苯砜，4,4 ' - 双（4-氯苯基）磺酰基-1,1'-联苯和4,4'-二羟基二苯基砜，固含量为20-35％; 搅拌直到单体完全溶解，加热至100℃，加入成盐剂和二甲苯; 在加热的同时搅拌，使得成盐反应在系统中开始，其中系统温度控制在190℃和210℃之间。 当排出的水量达到理论值时，第一阶段的成盐反应结束; 将系统加热至230-236℃，并保持3-4小时以获得聚合物粘稠液体; 并精炼聚合物粘性液体以获得在分子链中含有不同结构单元的三元共聚物，其中三元共聚物的Tg可以通过改变两种含二氯单体的比例来调节。

公开(公告)号：US20120208977A1

公开(公告)日：2012-08-16

申请号：US13504064

申请日：2010-12-10

申请人： Zhongwen Wu ,  Rongtang Ma ,  Xiangbin Zeng

发明人： Zhongwen Wu ,  Rongtang Ma ,  Xiangbin Zeng

IPC分类号： C08G75/20

CPC分类号： C08G75/23

摘要： A method for preparing series of terpolymer of poly (diphenyl ether sulfone) and poly (diphenyl ether diphenyl sulfone) comprises: adding high temperature organic solvent, stirring and heating; sequentially adding 4,4′-dihydroxydiphenyl, 4,4′-dichlorodiphenyl sulfone and 4,4′-Bis(4-chlorophenyl)sulfonyl-1,1′-biphenyl; after all the monomers are completely dissolved, heating to 100° C. and adding alkali metal carbonate salt-forming agent which is 5-10 mol % more than the amount of 4,4′-dihydroxydiphenyl added, and subsequently adding xylene; continuously heating and salt-forming reaction begins in the system, and controlling the temperature at 190˜210° C.; then heating to 230˜236° C., and maintaining for 3-4 hours to obtain polymer viscous liquid; and refining the polymer viscous liquid to obtain a terpolymer containing different structural units in the molecular chain, wherein the Tg of the terpolymer can be regulated by changing the ratio of the two dichloro-containing monomers.

摘要翻译： 一种制备聚（二苯基醚砜）和聚（二苯醚二苯基砜）三元共聚物的方法包括：加入高温有机溶剂，搅拌加热; 依次加入4,4'-二羟基二苯基，4,4'-二氯二苯砜和4,4'-双（4-氯苯基）磺酰基-1,1'-联苯; 在所有单体完全溶解后，加热至100℃，加入碱金属碳酸盐形成剂，其比加入的4,4'-二羟基联苯的量多5-10mol％，随后加入二甲苯; 在系统中开始连续加热和成盐反应，并控制温度在190〜210℃。 然后加热至230〜236℃，保持3-4小时得到聚合物粘稠液体; 并精炼聚合物粘性液体以获得在分子链中含有不同结构单元的三元共聚物，其中三元共聚物的Tg可以通过改变两种含二氯单体的比例来调节。

公开(公告)号：US20120202967A1

公开(公告)日：2012-08-09

申请号：US13501356

申请日：2010-10-26

申请人： Zhongwen Wu ,  Rongtang Ma

发明人： Zhongwen Wu ,  Rongtang Ma

IPC分类号： C08G75/23

CPC分类号： C08G75/23

摘要： A method for preparing terpolymer of poly (biphenyl sulfone ether) and poly (ether sulfone) comprises: adding high-temperature organic solvent into a flask, stirring and heating to 80° C., adding 4,4′-dichlorodiphenylsulfone,4,4′-Bis(4-chlorophenyl)sulfonyl-1,1′-biphenyl and 4,4′-dihydroxydiphenylsulfone with solid content of 20-35%; stirring until monomers are completely dissolved, heating to 100° C., adding salt-forming agent and xylene; stirring while heating so that salt-forming reaction begins in the system, wherein the system temperature is controlled between 190° C. and 210° C.; when the amount of water discharged reaches the theoretical value, the first stage of salt-forming reaction is finished; heating the system to 230-236° C., and maintaining for 3-4 hours to obtain polymer viscous liquid; and refining the polymer viscous liquid to obtain a terpolymer containing different structural units in the molecular chain, wherein the Tg of the terpolymer can be regulated by changing the ratio of the two dichloro-containing monomers.

摘要翻译： 制备聚（联苯砜醚）和聚（醚砜）三元共聚物的方法包括：向烧瓶中加入高温有机溶剂，搅拌加热至80℃，加入4,4'-二氯二苯砜，4,4 ' - 双（4-氯苯基）磺酰基-1,1'-联苯和4,4'-二羟基二苯基砜，固含量为20-35％; 搅拌直到单体完全溶解，加热至100℃，加入成盐剂和二甲苯; 在加热的同时搅拌，使得成盐反应在系统中开始，其中系统温度控制在190℃和210℃之间。 当排出的水量达到理论值时，第一阶段的成盐反应结束; 将系统加热至230-236℃，并保持3-4小时以获得聚合物粘稠液体; 并精炼聚合物粘性液体以获得在分子链中含有不同结构单元的三元共聚物，其中三元共聚物的Tg可以通过改变两种含二氯单体的比例来调节。